KR20040044960A - Process for producing poly(ethylene-aromatic dicarboxylate ester) resin and resin product - Google Patents

Abstract

Process for producing poly(ethylene-aromatic dicarboxylate ester) resin comprises subjecting a diester of an aromatic dicarboxylic acid and an ethylene glycol to condensation-polymerization in the presence of a catalyst comprising a mixture of titanium- and phosphorus- compounds. Process for producing poly(ethylene-aromatic dicarboxylate ester) resin comprises subjecting a diester of an aromatic dicarboxylic acid and an ethylene glycol to condensation-polymerization in the presence of a catalyst. The catalyst comprises a mixture of titanium- and phosphorus- compounds, and is obtained by regulating the concentration of P and Ti atoms of a reaction product of, or an unreacted mixture of, a P-containing compound component and a Ti-containing compound component. The titanium compound component contains one or more Ti-alkoxide compounds and a reaction product between a Ti-alkoxide and an aromatic polycarboxylic acid or its anhydride. The P-containing compound component contains at least one compound represented by general formula (1), (2) and (3). [Image] R 1>, R 2>, R 3>1-4C alkyl group; X : -CH 2- or group represented by (1a); R 4>2-18C alkyl or 6-20C aryl group; n : 1 or 2; p : 0 or 1 (when n = 1), and 0 (when n = 2); m, ma, mb : 0 or 1. The amount of the constituents of the catalyst satisfy the following relationships. 2 = M r i= 15 (a) 1 = (M p/ M r i) = 15 (b) 10 = (M r i+ M p) = 100 (c) M r iratio of the amount of Ti (mmol) contained in the catalyst to the total amount of mol of ethylene-aromatic dicarboxylate ester contained in the poly(ethylene-aromatic dicarboxylate ester); and M p : ratio of the amount of P (mmol) contained in the catalyst to the total amount of mol of ethylene-aromatic dicarboxylate ester contained in the poly(ethylene-aromatic dicarboxylate ester).

Description

Process for producing poly (ethylene-aromatic dicarboxylate ester) resin and resin product {PROCESS FOR PRODUCING POLY (ETHYLENE-AROMATIC DICARBOXYLATE ESTER) RESIN AND RESIN PRODUCT}

Poly (ethylene aromatic carboxylate ester) resins (hereinafter referred to as polyester resins) such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate have excellent mechanical properties, good heat resistance, good electrical It is widely used as a material for forming a shaped body having insulating properties and excellent chemical resistance and using the above-described physical properties such as fibers and bottle-shaped molded articles.

As a method for producing polyethylene terephthalate, for example, terephthalic acid is directly esterified with ethylene glycol, lower alkyl esters of terephthalic acid such as dimethyl terephthalate are transesterified with ethylene glycol, or terephthalic acid is reacted with ethylene oxide, There is a known method of forming ethylene glycol esters of terephthalic acid and / or polymers of low polymerization degree and heating the reaction product under reduced pressure to polycondensation until the desired degree of polymerization is reached.

In the production of polyester resins such as polyethylene terephthalate, polycondensation catalysts are generally used in order to allow the polymerization reaction to proceed smoothly. The polycondensation reaction rate and the quality of the polymer obtained are significantly affected by the type of polycondensation catalyst. Various metal compounds are known as polycondensation catalysts. Among these metal compounds, antimony (Sb) compounds such as antimony trioxide are widely used because they are inexpensive, have high polymerization activity, and the polymer obtained has a relatively good color tone. However, when the Sb compound is used as the polymerization catalyst, the proportion of the compound is reduced while forming metallic Sb or other foreign matter during the polycondensation reaction, so that the obtained polymer has a dark color and / or becomes unstable in the manufacturing process, There is a problem that the quality of the molded article produced from the resin obtained is poor.

When the Sb compound is used as a polycondensation catalyst for polyester, and the obtained polyester resin is continuously melt spun for a long time, foreign matter (hereinafter also referred to as spinneret foreign material) is deposited and accumulated around the spinning orifice, and the molten polymer stream There is a problem in that bending occurs in the filament and / or filament yarn breakage occurs in the obtained filament yarn in the spinning and stretching step.

As polycondensation catalysts other than an antimony compound, the titanium compound, such as a germanium compound and tetra-n-butoxy titanium, is proposed. Germanium compounds are quite expensive, and there is a problem that the production cost of polyester is increased. When the titanium compound is used as the polycondensation catalyst, the phenomenon of depositing foreign matter around the spinning orifice during melt spinning of the obtained polyester resin is suppressed. In this case, however, a known problem inherent in titanium compounds arises, in which the polyester itself obtained is colored yellow and / or the thermal stability of the melt of the polyester resin obtained is poor.

In order to solve the coloring problem of the polyester resin resulting from a polymerization catalyst, coloring to yellow is generally suppressed by adding a cobalt compound to polyester. Although the color tone (color value b) of the polyester can be reliably improved by the addition of the cobalt compound, the melt thermal stability of the polyester is further lowered by the addition of the cobalt compound, which leads to a known problem of promoting decomposition of the polymer. Occurs.

Japanese Patent Publication No. 48-2229 discloses titanium hydroxide as another titanium compound used in polycondensation catalysts of polyester resins, while Japanese Patent Publication No. 47-26597 uses α-titanic acid as a catalyst for producing polyester. Is disclosed. However, in the former method, titanium hydroxide is not easily powdered, while in the latter method, the physical properties of the α-titanic acid are easily changed and storage and handling are not easy. Therefore, these methods are not suitable for use in the industrial field, and also it is difficult to obtain a good color tone (color value b).

Japanese Patent Publication No. 59-46258 discloses the use of a product obtained by reacting a titanium compound with trimellitic acid as a polycondensation catalyst for producing polyester, and Japanese Patent Application Laid-Open No. 58-38722 It is disclosed to use a product obtained by reacting a titanium compound with a phosphite ester as a polycondensation catalyst for preparing an ester. Even if the thermal stability of the melt of the polyester is improved to some extent using the polymerization catalyst, the polymer obtained has a poor color tone (color value b), so that further color tone (color value b) improvement of the polyester is required. The use of antimony as a catalyst is an effective way to suppress deposits of spinneret debris. However, according to the method without antimony, the polyester resins and polyester resin products obtained, in particular polyester fibers, have an unsatisfactory color tone. Therefore, it is usually difficult to put the antimony-free catalyst into practical use.

In addition, the polyester resins are recovered using the aromatic dicarboxylate esters obtained by recovering the used polyester products (for example, fibers, films and bottles), and then washing, pulverizing and further depolymerization. It is known how to play it. In this case, there is also a need for the development of a process for producing recycled polyesters with good transparency and good color tone.

The present invention relates to a method for producing a poly (ethylene aromatic carboxylate ester) resin using a polycondensation catalyst obtained from a titanium compound and a phosphorus compound, a resin obtained by the above method, and a product thereof. More specifically, the present invention provides a method of using a polycondensation catalyst obtained from a titanium compound and a phosphorus compound, without forming foreign matters derived from the polycondensation catalyst (or forming less foreign matters), excellent transparency and excellent It relates to a process for producing poly (ethylene aromatic carboxylate ester) resins having a color tone and good melt stability, resins obtained thereby, and molded articles thereof, such as fibers, films and bottle-shaped molded articles.

Summary of the Invention

It is an object of the present invention to provide a process for the efficient production of poly (ethylene aromatic carboxylate ester) resins containing reduced amounts of impurities and having good transparency, high thermal stability of the melt and good color tone, the polys obtained thereby (Ethylene aromatic carboxylate ester) resins, and various molded articles obtained using the resins.

The process for producing the poly (ethylene aromatic carboxylate ester) resin of the present invention comprises polycondensing a diester of aromatic dicarboxylic acid with ethylene glycol in the presence of a catalyst system,

The catalyst system contains at least one selected from the group consisting of:

(1) a titanium compound component comprising at least one member selected from the group consisting of titanium alkoxides and reaction products of titanium alkoxides and aromatic polyvalent carboxylic acids or anhydrides thereof, and (2a) selected from compounds represented by the following formula (1): Unreacted mixtures and reaction products of phosphorus compound components comprising at least one species:

[Wherein, R ¹ , R ² and R ³ each independently and independently of one another represent an alkyl group having 1 to 4 carbon atoms, and X represents a —CH ₂ — group or a group represented by the following general formula (1a):

]; And

(1) an unreacted mixture of the above-described titanium compound component and (2b) a phosphorus compound component comprising at least one member selected from phosphorus compounds represented by the following formulas (2) and (3):

[Wherein, R ⁴ represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms, and n represents an integer of 1 or 2, when n represents 1, p is an integer of 0 or 1, and n When this 2 is represented, p represents 0], and

[Wherein m, ma and mb each independently and independently of each other represent an integer of 1 or 2];

The catalyst system satisfies the following conditional formulas (a), (b) and (c):

(a) 2 ≦ M _Ti ≦ 15

(b) 1 ≤ (M _p / M _Ti ) ≤15

(c) 10 ≦ (M _Ti + M _p ) ≦ 100

[In the above condition formulas (a), (b) and (c), M _Ti is contained in the catalyst system for the total amount (molar units) of the ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester). Represents the ratio of the amount of titanium elements (millimolar units) incorporated, and M _p is the phosphorus contained in the catalyst system relative to the total amount (mol units) of the ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester) Ratio of the amount of elements (millimolar units)].

According to the method for producing a poly (ethylene aromatic dicarboxylate ester) resin of the present invention, a diester of an aromatic dicarboxylic acid and ethylene glycol is optionally produced by a diesterization reaction of an aromatic dicarboxylic acid and ethylene glycol. Additionally included.

The method for producing a poly (ethylene aromatic dicarboxylate ester) resin of the present invention optionally comprises a diester of aromatic dicarboxylic acid and ethylene glycol by transesterification of dialkyl ester of aromatic dicarboxylic acid and ethylene glycol. It further includes manufacturing.

In the method for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the transesterification reaction of the dialkyl ester of the aromatic dicarboxylic acid and ethylene glycol is preferably at least unreacted or reacted with the titanium compound component (1 Is carried out in the presence of; The resulting reaction mixture obtained from the transesterification reaction and containing a diester of aromatic dicarboxylic acid and ethylene glycol, does not react or reacts with at least the unreacted or reacted titanium compound component (1) contained in the reaction mixture. The polycondensation reaction is carried out in the presence of a catalyst system containing one phosphorus compound component (2a) or unreacted phosphorus compound component (2b).

In the method for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the aromatic dicarboxylic acid is preferably terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 5-sulfoisophthalate metal salt and 5- Sulfoisophthalate onium salts.

In the method for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the dialkyl ester of the aromatic dicarboxylic acid is preferably dimethyl terephthalate, dimethyl isophthalate dimethyl naphthalate, diethyl terephthalate, di Ethyl isophthalate and diethyl naphthalate.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the titanium alkoxide for the titanium compound component (1) is preferably selected from a titanium compound represented by the following general formula (4):

[Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently and independently of each other represent an alkyl or phenyl group having 2 to 10 carbon atoms and m _c represents an integer of 1 to 4].

In the process for preparing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the aromatic polyhydric carboxylic acid for the titanium compound component (1) is preferably selected from compounds represented by the following general formula (5):

[Wherein, n _a represents an integer of 2 to 4].

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the transesterification reaction is preferably carried out under a pressure of 0.05 to 0.20 MPa.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the dialkyl ester of the aromatic dicarboxylic acid to be treated by the transesterification reaction preferably uses dimethyl terephthalate as the di-acid of the aromatic dicarboxylic acid. It is contained in an amount of 80 mol% or more based on the total molar amount of the alkyl ester.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the dialkyl ester of aromatic dicarboxylic acid to be treated by transesterification is preferably recovered by depolymerization of polyalkylene terephthalate. The dialkyl terephthalate is contained in an amount of 70 mol% or more based on the total molar amount of the dialkyl ester of the aromatic dicarboxylic acid.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the recovered dialkyl terephthalate preferably contains a 2-hydroxyterephthalic acid in a controlled content of 2 ppm or less.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the catalyst system preferably comprises an unreacted mixture of titanium compound component (1) and phosphorus compound component (2a) or (2b);

The titanium compound component (1) is added to the reaction system in its entirety before or at the beginning of the transesterification reaction;

The phosphorus compound component (2a) or (2b) is added to the reaction system obtained from the transesterification reaction in its entirety before or at the beginning of the polycondensation reaction.

In the process for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the catalyst system preferably comprises a reaction product of the titanium compound component (1) and the phosphorus compound component (2a);

The catalyst system is added to the reaction system in its entirety before or at the beginning of the transesterification reaction;

After the transesterification reaction is completed, the obtained reaction mixture is subjected to a polycondensation reaction.

In the method for producing a poly (ethylene aromatic dicarboxylate ester) resin of the present invention, preferably, part of the titanium compound component (1) or the titanium compound component (1) and the phosphorus compound component (2a) before the transesterification reaction A portion of the reaction product, or a portion of the phosphorus compound component (2b) is added to the reaction system and the remainder of the catalyst components described above in one or more stages during and after the transesterification reaction and before and during the polycondensation reaction Is added to the reaction system.

In the method for producing the poly (ethylene aromatic dicarboxylate ester) resin of the present invention, preferably, the entire amount of the phosphorus compound component (2a) is added to the diesterization reaction system before the start of the diesterization reaction, or the phosphorus compound component A portion of (2a) is added to the diesterization reaction system before the start of the reaction, and the remaining portion of the phosphorus compound component (2a) is one or more steps during and after the diesterization reaction and before and during the start of the polycondensation reaction. Is added to the reaction system.

The poly (ethylene aromatic dicarboxylate ester) resin of the present invention is produced by the method for producing a poly (ethylene aromatic dicarboxylate ester) resin as described above.

The poly (ethylene aromatic dicarboxylate ester) resin of the present invention optionally further contains an antioxidant hindered phenol compound in an amount of 1% by mass or less.

In the method for producing a poly (ethylene aromatic dicarboxylate ester) resin of the present invention, the poly (ethylene aromatic dicarboxylate ester) resin preferably has 5/1000 mol% or less of antimony element and germanium element, respectively. In the formulated content.

The polyester fiber of this invention contains the above-mentioned poly (ethylene aromatic dicarboxylate ester) resin.

In the polyester fiber of the present invention, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as a main component.

The polyester film of this invention contains the above-mentioned poly (ethylene aromatic dicarboxylate ester) resin.

In the polyester film of the present invention, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as a main component.

The bottle-shaped polyester molded article of the present invention contains the aforementioned poly (ethylene aromatic dicarboxylate ester) resin.

In the bottle-shaped polyester molded article of the present invention, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as a main component.

Best Modes in the Practice of the Invention

In the process of the present invention, poly (ethylene aromatic carboxylate ester) resins are prepared by polycondensing diesters of aromatic dicarboxylic acids and ethylene glycol in the presence of a catalyst system.

The catalyst system used in the process of the invention comprises one or more selected from the group consisting of:

(1) a titanium compound component comprising at least one member selected from the group consisting of titanium alkoxides and reaction products of titanium alkoxides and aromatic polyvalent carboxylic acids or anhydrides thereof, and (2a) selected from compounds represented by the following formula (1): Unreacted mixtures and reaction products of phosphorus compound components comprising at least one species:

[Formula 1]

[Wherein, R ¹ , R ² and R ³ each independently and independently of one another represent an alkyl group having 1 to 4 carbon atoms, and X represents a —CH ₂ — group or a group represented by the following general formula (1a):

[Formula 1a]

]; And

(1) an unreacted mixture of the above-described titanium compound component and (2b) a phosphorus compound component comprising at least one member selected from phosphorus compounds represented by the following formulas (2) and (3):

[Formula 2]

[Wherein, R ⁴ represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms, and n represents an integer of 1 or 2; when n represents 1, p represents 0 or 1 and n is 2 represents p represents 0], and

[Formula 3]

[Wherein m, ma and mb each independently and independently of one another represent an integer 1 or 2].

The contents of the titanium element and phosphorus element contained in the catalyst system used in the process of the present invention are adjusted to satisfy the following conditional formulas (a), (b) and (c):

(a) 2 ≦ M _Ti ≦ 15

(b) 1 ≤ (M _p / M _Ti ) ≤15

(c) 10 ≦ (M _Ti + M _p ) ≦ 100

[In the above condition formulas (a), (b) and (c), M _Ti is contained in the catalyst system for the total amount (molar units) of ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester). Represents the ratio of the amount of titanium elements (millimolar units) incorporated, and M _p is the phosphorus contained in the catalyst system relative to the total amount (mol units) of the ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester) Ratio of the amount of elements (millimolar units)].

In the above condition (a), M _Ti is a value corresponding to the total amount of the titanium compound component used in the transesterification reaction and the polycondensation reaction in the method of the present invention. The value of M _Ti is preferably 2 or more and 15 or less, more preferably 3 or more and 10 or less, and most preferably 3 or more and 6 or less. If the value of M _Ti is less than 2, the yield of the desired polyester resin is sometimes insufficient, and the molecular weight of the polyester obtained sometimes does not reach the desired value. On the other hand, when the value of M _Ti exceeds 15, the thermal stability of the polyester obtained is insufficient, the molecular weight is significantly lowered, and sometimes the polyester resin is molded at high temperatures, for example, melt spinning, melt film molding or When processed by melt bottle molding, a molded article with desired mechanical properties cannot be obtained.

In the conditional formula (b), the value of M _Ti is as described above, and corresponds to the total amount of the phosphorus compound component (2a) or (2b) used in the transesterification and polycondensation reactions in the process of the present invention. to be. The ratio of M _p / M _Ti is preferably 15 or less, more preferably 2 or more and 15 or less, most preferably 4 or more and 10 or less. If the ratio M _p / M _Ti is less than 1, the obtained polyester resin has a yellow tint. On the other hand, when the ratio exceeds 15, the polycondensation activity of the catalyst system is not sufficient to obtain polyester, making it difficult to obtain a polyester having a desired molecular weight. When M _p / M _Ti is in the range of 1 to 15, the polymerization activity of the catalyst system for the diester of aromatic dicarboxylic acid and ethylene glycol is sufficiently high, so that a polyester resin having a desired molecular weight and a good color tone can be obtained.

Further, in the above conditional formula (c), the sum of M _Ti and M _p , (M _Ti + M _p ), is preferably 10 or more and 100 or less, more preferably 2 or more and 70 or less. If the value of (M _Ti + M _p ) is less than 10, the uniformity and molding processability of the quality of the polyester resin obtained become insufficient, and the obtained polyester resin uses an electrostatic impression process- Production yields become insufficient when molded. In addition, the film obtained does not have a uniform thickness, so that the film obtained has insufficient film-forming processability and insufficient impact resistance. On the other hand, when the value of (M _Ti + M _p ) exceeds 100, the obtained polyester resin contains foreign substances derived from the polymerization catalyst, resulting in insufficient transparency.

The aromatic dicarboxylic acid used in the process of the invention is preferably selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 5-sulfoisophthalate metal salts and 5-sulfoisophthalate onium salts.

The process of the present invention may further comprise the step of preparing the diester of the aromatic dicarboxylic acid and ethylene glycol by diesterization of the aromatic dicarboxylic acid with ethylene glycol.

The diesterization reaction of the aromatic dicarboxylic acid with ethylene glycol is carried out in the absence of a catalyst or in the presence of a catalyst (for example, an alkali metal salt or an alkaline earth metal) under reaction conditions of a pressure of 0.05 to 0.20 MPa and a temperature of 230 to 280 ° C. Salt).

In another embodiment, the process of the present invention may further comprise preparing a diester of aromatic dicarboxylic acid and ethylene glycol by transesterification of the dialkyl ester of aromatic dicarboxylic acid with ethylene glycol.

In the transesterification reaction, the transesterification reaction of the aromatic dicarboxylic acid with the dialkyl ester of ethylene glycol is carried out at a temperature of 160 to 260 ° C. under a pressure of 0.05 to 0.20 MPa in the presence of a catalyst.

If the pressure during the transesterification reaction is less than 0.05 MPa, sometimes the reaction may not be sufficiently promoted by the catalysis of the titanium compound component (1). On the other hand, when the pressure exceeds 0.20 MPa, a large amount of diethylene glycol may be produced as a by-product, so that the obtained polymer may exhibit unsatisfactory physical properties, for example, unsatisfactory thermal stability.

In the process of the invention, when using dialkyl esters of aromatic dicarboxylic acids, the alkyl group preferably has 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group. Preferred dialkyl esters of aromatic dicarboxylic acids used in the process of the invention are preferably selected from dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, diethyl terephthalate, diethyl isophthalate and diethyl naphthalate .

In the process of the present invention, the dialkyl ester of aromatic dicarboxylic acid to be treated by transesterification may contain dimethyl terephthalate in an amount of at least 80 mol% relative to the total molar amount of dialkyl ester of aromatic dicarboxylic acid. .

The dialkyl ester of the aromatic dicarboxylic acid to be treated by the transesterification reaction contains 70 mol% of the dialkyl terephthalate recovered by depolymerization of the polyalkylene terephthalate relative to the total molar amount of the dialkyl ester of the aromatic dicarboxylic acid. It can contain in the above amount.

The recovered dialkyl terephthalate preferably contains a 2-hydroxyterephthalic acid in a controlled content of 2 ppm or less.

In the process of the present invention, when the diester of aromatic dicarboxylic acid and ethylene glycol is prepared by transesterification of aromatic dialkyl ester and ethylene glycol, the transesterification is usually carried out in the presence of a catalyst. As a catalyst for the transesterification reaction, all or part of the catalyst system for polycondensation used in the method of the present invention may be used.

That is, in the process of the present invention, the transesterification reaction of the aromatic dicarboxylic acid with the dialkyl ester of ethylene glycol is preferably not reacting with at least the phosphorus compound component (2a) or (2b) in the catalyst system or the phosphorus compound component (2a) Is carried out in the presence of a titanium compound component (1) reacted with; And

The phosphorus compound obtained from the transesterification reaction and containing a diester of aromatic dicarboxylic acid and ethylene glycol is unreacted or reacted with at least the unreacted or reacted titanium compound component (1) contained in the reaction mixture. The polycondensation reaction treatment is carried out in the presence of a catalyst system comprising component (2a) or unreacted phosphorus compound component (2b) to produce a poly (ethylene aromatic dicarboxylate ester) resin.

In the process of the present invention, the titanium compound component (1) constituting the catalyst system comprises at least one member selected from the group consisting of titanium alkoxides and reaction products of titanium alkoxides and aromatic polyhydric carboxylic acids or anhydrides thereof.

In the present invention, the titanium alkoxide used in the titanium compound component (1) constituting the catalyst system is preferably selected from titanium compounds represented by the following general formula (4):

[Formula 4]

[Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently and independently of each other represent an alkyl or phenyl group having 2 to 10 carbon atoms and m _c represents an integer of 1 to 4]. As the titanium alkoxide, for example, tetraisopropoxytitanium, tetrapropoxytitanium, tetra-n-butoxytitanium, tetraethoxytitanium, tetraphenoxycitane, octaalkyl trititanate and hexaalkyl dititanate are preferable. Is used.

In the process of the present invention, the aromatic polyhydric carboxylic acid used in the titanium compound component (1) constituting the catalyst system is selected from compounds represented by the following general formula (5):

[Formula 5]

[Wherein, n _a represents an integer of 2 to 4].

The aromatic polyhydric carboxylic acid or anhydride thereof is preferably selected from phthalic acid, trimellitic acid, hemimelitic acid, pyromellitic acid and anhydrides thereof.

The reaction of the titanium alkoxide with the aromatic polyhydric carboxylic acid (or anhydride thereof) mixes the aromatic polyhydric carboxylic acid or its anhydride with a solvent to dissolve all or part of the aromatic polyhydric carboxylic acid in the solvent, and the titanium alkoxide is By dropwise addition to the mixed solution and held at a temperature of 0 to 200 ° C. for at least 30 minutes, preferably at 30 to 150 ° C. for 40 to 90 minutes. The reaction pressure is not particularly limited and may be normal pressure. The solvent is selected from those capable of dissolving some or all of the aromatic polyhydric carboxylic acid or its anhydride, preferably from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene and xylene.

The reaction molar ratio of titanium alkoxide to aromatic polyvalent carboxylic acid or anhydride thereof is not particularly limited. However, if the proportion of titanium alkoxide is too high, the color tone of the polyester obtained may be poor and the softening point may be low. On the other hand, if the ratio of titanium alkoxide is too low, the polycondensation reaction sometimes does not proceed well. Therefore, the reaction molar ratio of titanium alkoxide to aromatic polyvalent carboxylic acid or anhydride thereof is preferably adjusted within the range of 2/1 to 2/5.

The reaction product obtained by the above reaction is reacted with the above-mentioned phosphorus compound component 2a as it is, or the reaction product is purified by recrystallization with a solvent containing acetone, methyl alcohol and / or ethyl acetate, and then the phosphorus compound component Can react with (2a).

In one embodiment of the catalyst system used in the process of the invention, an unreacted mixture or reaction product of titanium compound component (1) and phosphorus compound component (2a) is used. Phosphorus compound component (2a) contains 1 or more types chosen from the phosphorus compound represented by the said General formula (1).

The phosphorus compound (phosphonate compound) represented by Formula 1 is preferably carbomethoxymethanesulfonic acid, carboethoxymethanesulfonic acid, carbopropoxymethanesulfonic acid, carbobutoxymethanesulfonic acid, carbome Dimethyl ester, diethyl ester, dipropyl ester of oxy-phosphono-phenylacetic acid, carboethoxy-phosphono-phenylacetic acid, carbopropoxy-phosphono-phenylacetic acid and carbobutoxy-phosphono-phenylacetic acid And dibutyl ester.

The phosphorus compound (phosphonate compound) represented by the formula (1) reacts relatively gently with the titanium compound component (1), thus extending the duration of the catalytic activity of the titanium compound during the polycondensation reaction, and adding during the polyester polymerization reaction. It is possible to reduce the amount of catalyst system that becomes. Even if a large amount of stabilizer is added to the catalyst system containing the phosphorus compound of the formula (1), the thermal stability of the obtained polyester is not lowered, and the color tone is not insufficient.

The reaction product of the titanium compound component (1) and the phosphorus compound component (2a) is a phosphorus compound component (2a), for example, by mixing a phosphorus compound component (2a) containing one or more selected from the phosphorus compounds of the formula (1) with a solvent. All or a part of)) is dissolved in a solvent, the titanium compound component (1) is added dropwise to the mixed solution, and the reaction system is carried out at a temperature of 50 to 200 ° C., preferably at 70 to 150 ° C. for 1 minute to 4 hours, It is preferably prepared by holding for 30 minutes to 2 hours. In the reaction, the reaction pressure is not particularly limited and may be any one of a pressure of (0.1 to 0.5 MPa), an atmospheric pressure and a reduced pressure (0.001 to 0.1 MPa), but the reaction is usually performed under ambient atmospheric pressure.

The solvent for the phosphorus compound component (2a) of the general formula (1) used in the reaction for preparing the catalyst is not particularly limited as long as it can dissolve at least part of the phosphorus compound component (2a). For example, a solvent containing at least one selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene and xylene is preferably used. In particular, the same compound as the glycol component constituting the finally obtained polyester is preferably used as the solvent.

In the reaction for preparing the catalyst, preferably, the ratio of the titanium compound component (1) to the phosphorus compound component (2a) in the reaction system is adjusted to convert the molar amount (m _Ti ) to phosphorus calculated in terms of the titanium atom of the titanium compound component (1). Reaction of the titanium compound component (1) and the phosphorus compound component (2a) contained in the catalyst obtained by the reaction molar ratio, m _Ti / m _p of the molar amount (m _p ) calculated in terms of phosphorus atoms of the compound component (2a) In the product is in the range of 1: 1 to 1: 3, preferably 1: 1 to 1: 2.

The reaction product of the titanium compound component (1) and the phosphorus compound component (2a) can be used as a catalyst for producing polyester without purification after separation from the reaction system using a method such as centrifugal sedimentation or filtration. Alternatively, the separated reaction product can be used as a postcatalyst which is purified by recrystallization with a recrystallization agent such as acetone, methyl alcohol and / or water. The reaction mixture containing the reaction product can also be used as it is as the catalyst containing mixture without separating the reaction product from the reaction system.

In the catalyst system used in the method of the present invention, the titanium compound component (1) and the phosphorus compound component (2a) can be used as the unreacted mixture. In this case, the molar amount (m _Ti ) to the phosphorus of the phosphorus compound component (2a) calculated in terms of the titanium atom of the titanium compound component (1) by adjusting the ratio of the titanium compound component (1) to the phosphorus compound component (2a) The ratio of molar amounts, m _Ti / m _p , calculated in terms of atoms (m _p ) is brought into the range of 1: 1 to 1:15, more preferably 1: 2 to 1:10.

In another aspect of the catalyst used in the process of the invention, the titanium compound component (1) is used after mixing with the phosphorus compound component (2b) containing at least one selected from the phosphorus compounds represented by the formula (2) or (3). .

Specific examples of the phosphorus compound represented by the formula (2) include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, tolylphosphonic acid, and xylyl when p represents 0. Phosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonic acid, 2-carboxymethylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2 , 4-dicarboxyphenyl phosphonic acid, 2,5-dicarboxyphenyl phosphonic acid, 2,6-dicarboxyphenyl phosphonic acid, 3,4-dicarboxyphenyl phosphonic acid, 3,5-dicarboxyphenyl phosphonic acid, 2 , 3,4-tricarboxyphenyl phosphonic acid, 2,3,5-tricarboxyphenyl phosphonic acid, 2,3,6-tricarboxyphenyl phosphonic acid, 2,4,5-tricarboxyphenyl phosphonic acid and 2,4 , 6-tricarboxyphenyl phosphonic acid. Of these compounds, monoarylphosphonic acid is preferred.

Specific examples of other phosphorus compounds represented by the formula (2) include monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, and monononyl phosphate when p represents 1 , Monodecyl phosphate, monododecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methyl) phenyl phosphate, mono (4-ethyl) phenyl phosphate, mono (4- Propyl) phenyl phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate and monoanthryl phosphate.

Specific examples of the phosphorus compound of formula 3 include tri (hydroxyethoxy) phosphate and tri (hydroxyethoxyethoxy) phosphate.

In the catalyst system used in the method of the present invention, the titanium compound component (1) and the phosphorus compound component (2b) can be used in their unreacted mixture. In this case, the mixing of the titanium compound component (1) with the phosphorus compound component (2b) is preferably controlled, and the molar amount (m _Ti ) calculated from the titanium atom of the titanium compound component is converted to the phosphorus atom of the phosphorus compound component. The ratio of the calculated molar amount (m _p ), m _Ti / m _p, is brought into the range of 1: 1 to 1:15, more preferably 1: 2 to 1:10.

Phosphorus compound components (2a) and (2b) containing phosphorus compounds of the formulas (1), (2) and (3), reaction products with titanium compound component (1) in transesterification reactions of aromatic aromatic dicarboxylic acids with dialkyl esters of ethylene glycol or not When coexisting as a reaction mixture, they do not adversely affect the transesterification reaction, and also exhibit a strong catalytic activity with the titanium compound component (1) in the polycondensation reaction of the diester of aromatic dicarboxylic acid and ethylene glycol.

In the process for producing the polyesters of the present invention, polymerization starting materials (or their oligomers (oligomers) thereof) containing diesters of aromatic dicarboxylic acids and ethylene glycol are polycondensed in the presence of a catalyst.

The polycondensation reaction is preferably carried out at a temperature of 230 to 320 ° C. under normal or reduced pressure, preferably 0.05 Pa to 0.2 MPa, or under combined conditions for 15 to 300 minutes.

In the process of the present invention, when the catalyst system comprises an unreacted mixture of titanium compound component (1) and phosphorus compound component (2a) or (2b),

The whole amount of the titanium compound component (1) is added to the reaction system before or at the beginning of the transesterification reaction,

The entire amount of the phosphorus compound component (2a) or (2b) is added to the reaction system obtained from the transesterification reaction before or at the beginning of the polycondensation reaction.

In the case where the catalyst system comprises a reaction mixture of the titanium compound component (1) and the phosphorus compound component (2a),

The whole amount of the catalyst system is added to the reaction system before or at the beginning of the transesterification reaction,

After the transesterification reaction is completed, the obtained reaction mixture is subjected to the polycondensation reaction.

In the process of the present invention, when the diester of aromatic dicarboxylic acid and ethylene glycol is produced by a transesterification reaction, optionally, part of the titanium compound component (1) or the titanium compound component before the transesterification reaction A portion of the reaction product of (1) and phosphorus compound component (2a), or a portion of phosphorus compound component (2a) is added to the reaction system and at least one step during and after the transesterification reaction and before and during the polycondensation reaction. The remainder of the catalyst component described above is added to the reaction system.

In the process of the present invention, when the diester of aromatic dicarboxylic acid and ethylene glycol is produced by diesterization reaction, in some cases, the total amount of phosphorus compound component (2a) is diester before the start of the diesterization reaction. Or a portion of the phosphorus compound component (2a) is added to the diesterization reaction system before the start of the reaction, and the remaining portion of the phosphorus compound component (2a) is during and after the diesterization reaction, and the polycondensation reaction Is added to the reaction system in one or more steps before and during the start of the reaction.

According to the process of the present invention as described above, a poly (ethylene aromatic carboxylate ester) resin having a good color tone is obtained without forming foreign matter (or forming less foreign matter) from the catalyst system used.

If desired, reaction stabilizers such as trimethyl phosphate may be added to the polyester resins of the present invention at any stage during the preparation of the polyester resin, and, if desired, antioxidants, ultraviolet absorbers, flame retardants, fluorescent whitening agents, quenchers. At least one selected from additives such as color control agents, antifoaming agents and the like may be added. It is particularly preferable that the polyester contains an antioxidant containing at least one member selected from non-free phenol compounds, the content of which is preferably 1% by mass or less based on the mass of the polyester. If the content exceeds 1% by mass, the problem sometimes arises that the thermal deterioration of the antioxidant itself lowers the quality of the product obtained. Non-free phenolic compounds for antioxidants used in the present invention include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane , 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert -Butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzene) isophthalic acid, triethyl glycol-bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propio Nate], 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate]. These minor oil phenolic antioxidants are preferably used in combination with thioether secondary antioxidants.

The method of adding the non-free phenolic antioxidant to the polyester is not particularly limited, but the non-free phenolic antioxidant is preferably added at any stage during or after the transesterification reaction and before the completion of the polycondensation reaction.

In order to finely adjust the color tone of the obtained polyester, a color control agent containing at least one selected from organic and inorganic blue pigments such as azo, triphenylmethane, quinoline, anthraquinone and phthalocyanine pigments is reacted at the production stage of the polyester. Can be added to. In the method of the present invention, of course, it is not necessary to use an inorganic blue pigment containing Co, which lowers the melting thermal stability of the polyester, as a color regulator. Thus, the polyesters obtained by the process of the invention are substantially free of cobalt.

In the polyester obtained by the method of the present invention, the L value obtained by the Hunter color system is usually 80.0 or more, and the b value is usually in the range of -2.0 to 5.0. If the L value of the polyester is less than 80.0, a high whiteness molded article that can be put to practical use cannot be obtained because the whiteness of the polyester sometimes obtained is poor. If the b value is less than -2.0, the blue tint increases because the obtained polyester has a lighter yellow tint. On the other hand, when the b value exceeds 5.0, the polyester obtained cannot sometimes be used for the production of practical moldings due to the strong yellow tint. The L value of the polyester obtained by the process of the invention is preferably at least 82, particularly preferably at least 83, and the b value is preferably in the range of -1.0 to 4.5, particularly preferably 0.0 to 0.4. .

The L value and b value of the polyester obtained by the method of the present invention are measured according to the following procedure. That is, the polyester sample is melted under vacuum at 290 ° C. for 10 minutes and molded into an aluminum plate having a thickness of 3.0 ± 1.0 mm. The polyester specimens are immediately quenched in ice water, dried at 160 ° C. for 1 hour, crystallized and placed on a white standard plate for colorimetric control. The color tone of the surface of the plate-shaped specimen on the standard plate was measured by Minolta Co., Ltd. Measure using a colorimeter such as Hunter-type color difference meter, CR-200.

Intrinsic viscosity of polyester in this invention is although it does not restrict | limit especially, Preferably it exists in the range of 0.50 to 1.0. If the intrinsic viscosity is within the above range, melt molding can be easily performed, and the molded article obtained is high in strength. The intrinsic viscosity is more preferably in the range of 0.52 to 0.9, particularly preferably 0.05 to 0.8.

The intrinsic viscosity of the polyester is measured at a temperature of 35 ° C. after dissolving the test polyester in ortho-chlorophenol.

Since polyesters prepared by solid-phase polycondensation are generally used for bottle preparation, the content of cyclic trimers of esters of ethylene glycol with aromatic dicarboxylic acids having an intrinsic viscosity of 0.70 to 0.90 contained in the polyester is 0.5% by weight. It is preferably at most%, and the content of acetaldehyde in polyester is at most 5 ppm.

The poly (ethylene aromatic dicarboxylate ester) resin produced by the process of the present invention is preferably at most 5/1000 mol%, more preferably at most 2/1000 mol%, of antimony and germanium elements as impurities. Contained in controlled content.

When the content of antimony and germanium elements in the polyester exceeds 5/1000 mol%, the obtained polyester has a darkish color characteristic of the antimony element, and the introduction of the germanium element increases the manufacturing cost of the obtained polyester. Cause problems such as.

As described above, the content of the antimony element and the germanium element in the poly (ethylene aromatic dicarboxylate ester) resin is the content of the antimony element and the germanium element in the diester of the aromatic dicarboxylic acid and ethylene glycol treated by the polycondensation reaction. By adjusting the content to 5/1000 mol% or less.

Polyester fibers can be made from the poly (ethylene aromatic dicarboxylate ester) resins of the present invention.

In this case, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as the main component.

Polyester films can be prepared from the poly (ethylene aromatic dicarboxylate ester) resins of the present invention.

In this case, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as the main component.

Bottle-shaped polyester molded articles can be made from the poly (ethylene aromatic dicarboxylate ester) resins of the present invention.

In this case, the poly (ethylene aromatic dicarboxylate ester) resin preferably contains polyethylene terephthalate as the main component.

In embodiment (1) of the process of the invention, the polyethylene terephthalate resin is controlled, preferably using a catalyst system, while adjusting the catalyst system to satisfy the above conditions (a), (b) and (c), preferably polycondensation As the substance, an ester of aromatic dicarboxylic acid and ethylene glycol containing at least 80 mol%, more preferably at least 85 mol% of ethylene terephthalate, is used, and the content of antimony and germanium elements is 5/1000 mol% or less, respectively. Manufacture by limiting. In the above embodiment (1), when the ester of the aromatic dicarboxylic acid and ethylene glycol is prepared by transesterification, dimethyl terephthalate is adjusted to occupy at least 80 mol% of the alkyl ester of the aromatic dicarboxylic acid. In the above transesterification reaction, part or all of the titanium compound component (1) of the catalyst system used in the process of the present invention is added to the transesterification system, and the transesterification reaction is carried out under a pressure of 0.05 to 0.20 MPa, and the resulting aromatic The ester of dicarboxylic acid and ethylene glycol is subjected to polycondensation reaction.

The polyethylene terephthalate resin obtained in embodiment (1) preferably contains ethylene terephthalate resin in an amount of at least 80 mol%, more preferably at least 85 mol%, and may be mixed with other resins other than ethylene terephthalate resin. have. Polyethylene terephthalate resin means a polyester having an ethylene terephthalate structure as the main repeating unit. As used herein, the main repeating unit contains ethylene terephthalate units in an amount of at least 80 mol%, more preferably at least 85 mol% of the total repeating units. When the polyethylene terephthalate resin is obtained by copolymerization with a third component other than the ethylene terephthalate component, the third component (copolymerization component) is an aromatic dicarboxylic acid other than terephthalic acid, such as 2,6-naphthalenedicarboxylic acid, Isophthalic acid or phthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid or decandicarboxylic acid; And cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid.

The polyester resin of embodiment (1) preferably has an intrinsic viscosity (o-chlorophenol, 35 ° C.) in the range of 0.50 to 0.80, more preferably 0.55 to 0.75, particularly preferably 0.60 to 0.70.

When the polyethylene terephthalate resin of embodiment (1) is used for film molding, for the purpose of improving handleability, it contains, as lubricant, inert particles having an average particle diameter of 0.05 to 5.0 μm in an amount of about 0.05 to 5.0 wt%. can do. For the purpose of maintaining the high transparency characteristic of the polyethylene terephthalate resin of the present invention, the smaller the particle size of the inert particles, the smaller the amount of the inert particles is better. Examples of inert particles used as lubricants include colloidal silica, porous silica, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, zirconia, kaolin, composite oxide particles, crosslinked polystyrene, crosslinked acrylic resin particles, crosslinked Methacryl resin particles and silicon particles are included. When polyethylene terephthalate resin is used in various molded articles such as films, fibers and bottles, various functional agents such as antioxidants, heat stabilizers, viscosity modifiers, plasticizers, color regulators, nucleating agents and ultraviolet absorbers as needed It may contain.

In embodiment (2) of the present invention, the diester of terephthalic acid and a diester of ethylene glycol are prepared by using a catalyst system containing an unreacted mixture or reaction product of titanium compound component (1) and phosphorus compound component (2a). Alkyl esters are preferably produced by transesterification of dimethyl terephthalate with ethylene glycol (pressure: 0.05 to 0.20 MPa), and the diesters are polycondensed to form polyethylene terephthalate resins. At this time, the composition of the catalyst system is adjusted to satisfy components (a), (b) and (c). Polyester fibers are made from polyethylene terephthalate resins.

The polyester resin preferably has an intrinsic viscosity in the range of 0.40 to 0.80, more preferably 0.45 to 0.75, particularly preferably 0.50 to 0.70. Inherent viscosity of less than 0.40 is undesirable because the fibers obtained may have insufficient strength. On the other hand, if the intrinsic viscosity exceeds 0.80, the intrinsic viscosity of the raw polymer may be excessively high, which may be uneconomical.

In embodiment (2) of the method of the present invention, the production method of the polyester fiber is not particularly limited, and a conventionally known melt spinning method of polyester can be used. For example, it is desirable to melt the polyester at a temperature in the range of 270 to 300 ° C. and spin the molten polyester while controlling the melt spinning rate within the range of 400 to 5000 m / min, wherein the fibers obtained have sufficient strength It can be wound up under stable conditions. The stretched fiber yarn can be produced by winding polyester fibers or continuously stretching the fibers without winding the fibers. Moreover, the polyester fibers of the present invention can be weight-treated with alkali to increase the flexibility of the fibers.

In the production of polyester fibers, the shape of the spin orifice of the spinneret is not particularly limited, and may be circular or non-circular, or spinning orifices for hollow fibers may be used.

In embodiment (3) of the present invention, diesters of aromatic dicarboxylic acids such as terephthalic acid and ethylene glycol or oligomers of the diesters are prepared, for example, by ester reaction of high purity terephthalic acid and ethylene glycol, The oligomer is subjected to a polycondensation reaction. In the polycondensation reaction, the diester or oligomer contains a reaction product of a titanium compound component containing a titanium alkoxide represented by the formula (4) and a phosphorus compound component containing a phosphorus compound represented by the formula (1) in a glycol solvent. It is polycondensed in the presence of a polycondensation catalyst system to produce a poly (ethylene aromatic dicarboxylate ester) resin. The poly (ethylene aromatic dicarboxylate ester) resin obtained is made into a polyester film via a film-forming step.

In embodiment (3), the molar ratio of phosphorus atoms to titanium atoms contained in the catalyst system is preferably 1.0 or more and less than 8.0, more preferably 2.0 or more and less than 7.0.

When the reaction product is contaminated with unreacted titanium compound component (1), the polyester resin obtained may have an unsatisfactory color tone. When the reaction product is contaminated with the unreacted phosphorus compound component (2a), the polycondensation reaction of the ester of terephthalic acid and ethylene glycol can be suppressed.

The reaction of the titanium compound component (1) and the phosphorus compound component (2a) proceeds by mixing the titanium compound component (1) and the phosphorus compound component (2a) and heating the mixture. The reaction product is usually in solution. In order to advance reaction uniformly, it is preferable to use the method by which the glycol solvent solution of the titanium compound component (1) and the glycol solvent solution of the phosphorus compound component (2a) are respectively produced, and a mixture is heated. If the reaction temperature is room temperature, a problem arises that the reaction proceeds insufficiently and the reaction requires an excessively long time. Therefore, in order to obtain the reaction product uniformly and efficiently, the reaction is preferably carried out at a temperature in the range of 50 to 200 ° C, and the reaction time is preferably in the range of 1 minute to 4 hours. When using ethylene glycol as glycol, it is preferable that reaction temperature exists in 50-150 degreeC range, and when using hexamethylene glycol as glycol, it is preferable that reaction temperature exists in 100-200 degreeC range. In this case, the reaction time is preferably in the range of 30 minutes to 2 hours.

The catalyst system used in embodiment (3) preferably satisfies the above condition (a), (b) and (c).

In embodiment (3), the polyester film melt-extrudes the poly (ethylene aromatic dicarboxylate ester) resin and quench the extruded resin melt stream to form an undrawn film, the unstretched film It can manufacture by biaxially stretching. After stretching, the obtained polyester film may be heat cured or relaxed heat treated as necessary.

As aromatic dicarboxylic acid, for example, terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid or ester-forming derivatives thereof can be used. .

It is also possible to use small amounts of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid or decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid to aromatic dicarboxylic acids. It can also be used in combination with an acid. In addition, ester-forming derivatives of the compounds described above may be used. It is also possible to use small amounts of cycloaliphatic glycols such as trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol or cyclohexane dimethanol, bisphenol, hydroquinone or 2,2 It is also possible to use -bis (4-β-hydroxyethoxyphenyl) propane in combination with ethylene glycol.

In addition, polyfunctional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane or pentaerythritol can be used in small amounts in combination with aromatic dicarboxylic acids.

In embodiment (3), the polyesters constituting the polyester film are preferably at least 80 mol%, preferably 90 mol%, of terephthalic acid or its ester-forming derivatives relative to 100 mol% of aromatic dicarboxylic acids. Polyethylene terephthalate is used in the above amounts and ethylene glycol or its ester-forming derivative is used in an amount of at least 80 mol%, preferably at least 90 mol% with respect to 100 mol% of aliphatic glycol. Particularly preferred is polyethylene terephthalate prepared via ester reaction such that terephthalic acid accounts for 80 mol% of all dicarboxylic acid components used as raw materials. Compared to polyethylene terephthalate prepared using dimethyl terephthalate as starting compound Thus, polyethylene terephthalate prepared using terephthalic acid as the starting compound does not require a transesterification catalyst and a stabilizer added to deactivate the transesterification catalyst. As a result, the interaction between the phosphorus compound and the titanium compound added as a stabilizer is suppressed, and there is an advantage that the amount of the titanium compound can be reduced.

Now, the process for producing the polyester through the esterification reaction will be described in detail.

(Esterification process)

First, in the preparation of polyesters, aromatic dicarboxylic acids are esterified with aliphatic glycols. For example, a slurry containing aromatic dicarboxylic acid and aliphatic glycol is prepared. The slurry usually contains 1.1 to 1.6 moles, preferably 1.2 to 1.4 moles of aliphatic glycol per mole of aromatic dicarboxylic acid. The slurry is fed continuously to the esterification process.

The esterification reaction is preferably carried out by a process carried out in a single step while self-circulating the reaction mixture or by a process in which two or more esterification reactors are combined in series with each other. In both cases, the reaction is carried out by removing the water produced during the reaction out of the reaction system using a rectification column under conditions where the aliphatic glycol is refluxed.

When the esterification reaction is carried out continuously in a single step while self-circulating the reaction mixture, the reaction is usually at a reaction temperature in the range from 240 to 280 ° C., preferably from 250 to 270 ° C., under a reaction pressure in the range from ambient atmospheric pressure to 0.3 MPa. Is performed. The reaction is preferably carried out until the degree of esterification reaches at least 90%, preferably at least 95%.

By the esterification step, an esterification reaction product (oligomer) of aromatic dicarboxylic acid and aliphatic glycol is obtained, and the degree of polymerization of the oligomer is preferably in the range of 4 to 10. The oligomers thus obtained are fed to the subsequent polycondensation step.

(Polycondensation Process)

In the polycondensation step, the oligomer obtained in the esterification step is polycondensed by heating to a temperature higher than the melting point of the polyester (usually 240 to 280 ° C) in the presence of the polycondensation catalyst described above. The polycondensation reaction is preferably performed while distilling out of the reaction system the unreacted aliphatic glycol and the aliphatic glycol produced during the polycondensation reaction.

The polycondensation reaction can be carried out in a single reaction vessel or can be carried out separately in a plurality of reaction vessels. When the polycondensation reaction is carried out in two stages, the polycondensation reaction in the first vessel is carried out at a reaction temperature in the range of 245 to 290 ° C., preferably 260 to 280 ° C., and 100 to 1 kPa, preferably 50 to 2 It is carried out under conditions of reaction pressure in the kPa range. The final polycondensation reaction in the second vessel is carried out under conditions of reaction temperature in the range of 265 to 300 ° C., preferably 270 to 290 ° C., and reaction pressure in the range of 1000 to 10 Pa, preferably 500 to 30 Pa. .

In the above manner, polyesters constituting the polyester film can be produced, and the obtained polyester can be molded into granules (chips) by being extruded in a molten state and then cooled. The polyester obtained preferably has an intrinsic viscosity (hereinafter referred to as IV) in the range of 0.40 to 0.80 dl / g, more preferably 0.50 to 0.70 dl / g.

The polyester film of the present invention may be a single layer film or a laminated film comprising two or more layers. In the case of laminated films, one or more layers may comprise the polyester film of the invention, preferably all layers comprise the polyester film of the invention.

Manufacturing conditions, such as stretching conditions in forming into a film, can be suitably established to correspond to physical properties such as surface properties, density and heat shrinkage of the desired film. For example, the unstretched film described above is uniaxially stretched (either longitudinally or transversely) at a draw ratio of at least 2.5 times, preferably at least 3 times, at a temperature within the range of [Tg-10] to [Tg + 60] ° C. , At a temperature in the range of Tg to [Tg + 70] ° C., at a stretching ratio of at least 2.5 times, preferably at least 3 times, stretching in a direction perpendicular to the stretching direction. The stretched film obtained as necessary can be further stretched in the longitudinal or transverse direction. The area draw ratio which is the product of the longitudinal draw ratio and the transverse draw ratio is preferably 9 or more, more preferably 12 to 35, particularly preferably 15 to 30. After stretching, the stretched film may be heat cured, and if necessary, the stretched film may be relaxed heat treated before or after the heat curing treatment. The thermosetting treatment is preferably carried out at a temperature within the range of [Tg + 70] to [Tm-10] ° C. (Tm: polyester melting point), for example, 180 to 250 ° C., and the heat curing time is 1 to 60 seconds. It is preferable to exist in the range.

In the polyester film of the present invention, inert particles having an average particle size of 0.05 to 5.0 µm may be added in an amount of about 0.05 to 50% by weight as a lubricant for the purpose of improving handling properties. Examples of inert particles to be added are colloidal silica, porous silica, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, zirconia, kaolin and composite oxide particles, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked meta Krill resin particles and silicon particles are included.

In embodiment (4) of the present invention, when the transalkylation reaction of the dialkyl ester of aromatic dicarboxylic acid with ethylene glycol is carried out in the presence of a catalyst system, when the polycondensation reaction is carried out to produce a polyester resin, polyalkylene Dimethyl terephthalate recovered by depolymerization of terephthalate is used in a proportion of at least 70% by weight of the dialkyl ester of the aromatic dicarboxylic acid. At this time, the catalyst system is preferably used after being manufactured to satisfy the above-described condition (a), (b) and (c).

In embodiment (4), the polyalkylene terephthalate to be depolymerized is preferably polyethylene terephthalate, for example a recovered bottle, a recovered polyester fiber product, a recovered polyester film product, and the preparation of said product. Recovered polyesters, such as waste polymers generated in the process, are particularly preferably used. When dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is used in an amount of less than 70% by weight, the proportion of the component derived from the recovered dimethyl terephthalate is contained in the finally obtained polyester or polyester fiber. Since less than 50% of the ingredients, environmentally friendly products reduce the impression. Therefore, it is not preferable. Dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is preferably used in an amount of at least 80% by weight, more preferably at least 90% by weight.

The method for preparing dimethyl terephthalate obtained by depolymerization of the polyalkylene terephthalate used in the present invention is not particularly limited, for example, by depolymerizing polyethylene terephthalate with ethylene glycol, transesterified with methanol, and obtained. Purified dimethyl terephthalate by recrystallization or distillation. The content of 2-hydroxyterephthalic acid in the impurities contained in dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is preferably 2 ppm or less.

The polyester produced by the above process can be used for the production of fibers, films and bottles. The fibers can be produced by the process described in embodiment (2) and the film can be produced by the process described in embodiment (3).

In embodiment (5) of the present invention, a polyethylene terephthalate film is produced by the method of the present invention. In this embodiment, the content of impurities contained in terephthalic acid (TA) used as starting material is controlled as follows: The content of monomethyl terephthalate (MMT) is controlled to 1000 ppm or less, and 4-carboxybenzaldehyde (4 The total content of -CBA), para-toluic acid (p-TA), benzoic acid (BA) and dimethyl hydroxy terephthalate (HDT) is controlled to 1 ppm or less. Terephthalic acid can be obtained by depolymerizing by heating the used polyester packaging material in alkylene glycol and hydrolyzing dimethyl terephthalate (DMT) obtained by transesterification of the depolymerization product with methanol. As the polycondensation catalyst system, a reaction product of a titanium alkoxide of formula (4) and a phosphorus compound of formula (1) is used. The ratio of the molar amount of phosphorus atoms to the molar amount of titanium atoms in the catalyst is preferably 1.0 or more and less than 8.0.

In embodiment (5), in order to obtain terephthalic acid containing MMT in an amount of 1000 ppm or less, the hydrolysis reaction of DMT is preferably in the range of 230 to 260 ° C under pressure in the range of 3.0 to 4.6 MPa (gauge pressure). At temperatures, more preferably under pressure in the range of 4.0 to 4.6 MPa (gauge pressure) for 2 to 3 hours at temperatures in the range of 250 to 260 ° C. MeOH produced during the hydrolysis reaction is removed together with the dimethyl ether produced as a byproduct by introducing a stripping vapor into the reactor.

The TA produced during the hydrolysis reaction is collected by suspending or dissolving in water, exiting the reactor and subject to a plurality of crystallization treatments and solid-liquid separation processes. The obtained TA cake can be subjected to esterification reaction and polycondensation reaction after drying, grinding and slurry preparation.

The content of MMT in terephthalic acid obtained by the above process is 1000 ppm, while the total content of 4-CBA, p-TA, BA and HDT is 1 ppm or less, so terephthalic acid is suitable as a polyester resin for films.

Since TA contains MMT in an amount of less than 1000 ppm, the glycol end of the polyethylene terephthalate obtained by the polycondensation reaction is blocked, and its thermal stability is improved. However, if the content exceeds 1000 ppm, the transparency of the polyethylene terephthalate obtained can be reduced.

In the polyethylene terephthalate resin of embodiment (5), it is preferable that the TA component accounts for 85 mol% with respect to the total acid component, and the ethylene glycol component accounts for 85 mol% with respect to the total diol component.

The total content of poly (alkylene aromatic dicarboxylate ester) resins other than polyethylene terephthalate, which may be contained in the polyethylene terephthalate of embodiment (5), is 15 mol% or less, and the acid component is 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, other isomers of naphthalenedicarboxylic acid, isophthalic acid, diphenyldica Aromatic dicarboxylic acid components such as carboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid and diphenylsulfondicarboxylic acid; Alicyclic dicarboxylic acid components such as hexahydroterephthalic acid and hexahydroisophthalic acid; Aliphatic dicarboxylic acid components such as adipic acid, sebacic acid and azelaic acid; And difunctional carboxylic acid components such as hydroxycarboxylic acids such as p-β-hydroxyethoxybenzoic acid and ε-oxycaproic acid. Diol components other than ethylene glycol include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 2, It may be at least one selected from 2-bis (4'-β-hydroxyphenyl) propane and bis (4'-β-hydroxyethoxyphenyl) sulfone. In addition, trifunctional or polyfunctional compounds may be copolymerized in amounts of up to 10%.

In embodiment (5), the stretched polyester film is prepared by melt extruding the polyester resin obtained by the above process and quenching the extruded melt stream to form an unstretched film and biaxially stretching the unstretched film. After stretching, the obtained polyester film is optionally heat treated and / or relaxed heat treated as necessary.

In embodiment (6) of the present invention, an alkyl aromatic dicarboxylate containing dimethyl terephthalate in an amount of 70% by weight or more by depolymerization, transesterification and hydrolysis of the polyester material used is carried out. To prepare an ester; Transesterification of the obtained alkyl aromatic dicarboxylate ester and ethylene glycol in the presence of a portion of the catalyst system; The remainder of the catalyst system is added to the obtained reaction mixture, and the ester or oligomer contained in the reaction mixture is polycondensed to prepare from a polyester resin produced by a process for producing a polyester resin. In this case, a mixture of the titanium compound component (1) and the phosphorus compound component (2a) is used as the catalyst system. After the titanium compound component (1) is used as a catalyst in the transesterification reaction, the phosphorus compound component (2a) is added for the polycondensation reaction of the obtained ester or oligomer. The catalyst preferably satisfies the conditions (a), (b) and (c) described above. In the polyester resin obtained, the content of ethylene terephthalate repeating units is preferably 80 mol% or more based on the total amount of the ester repeating units. The dicarboxylic acid component and diol component of the non-ethylene terephthalate repeating unit in the polyester may be the same as described in embodiment (5).

In the process of embodiment (6), dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is preferably a dialkyl ester of aromatic dicarboxylic acid, which is the starting material of the polyester, It is used in an amount of 50 mol% or more based on the total molar amount.

Preferred polyalkylene terephthalates are polyethylene terephthalates, particularly recovered polyesters such as recovered PET bottles, recovered polyester fiber products, recovered polyester film products and waste polymers generated in the manufacturing process of these products. It is preferably used.

When dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is used in an amount of 70 mass% or less, the proportion of the component derived from the recovered dimethyl terephthalate is contained in the finally obtained polyester or polyester fiber. Since less than 50% of the components used, the recycling efficiency of the polyester product used is insufficient. The content of dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate is preferably at least 80% by weight, more preferably at least 90% by weight relative to the total amount of the dialkyl aromatic dicarboxylate ester.

When recycled dimethyl terephthalate is used, the method for producing dimethyl terephthalate is not particularly limited. For example, in the process, polyethylene terephthalate is depolymerized with ethylene glycol, the material obtained is transesterified with methanol and the dimethyl terephthalate obtained is purified by recrystallization or distillation. Among the impurities contained in dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate, the content of 2-hydroxyterephthalic acid is preferably 2 ppm or less.

The intrinsic viscosity of the polyester usable in the polyester film is not particularly limited. Usually, it is preferably in the range of 0.50 to 0.80, more preferably 0.55 to 0.75, and particularly preferably 0.60 to 0.70. If the intrinsic viscosity is within the above range, the obtained film has sufficient mechanical strength, and the polymer for the film does not need to have an excessively increased intrinsic viscosity. Therefore, it is economically beneficial.

The manufacturing method of a polyester film is not specifically limited, A polyester film is manufactured by melt-extruding the polyester resin obtained by the said method, quenching a resin to form an unstretched film, and biaxially stretching the said unstretched film. can do. After stretching, the polyester film obtained can be heat cured and / or relaxed heat treated as necessary.

Embodiment (7) of the present invention includes a titanium compound component (1) and at least one member selected from phosphorus compounds of formulas (2) and (3) for the production of polyester resins having an ethylene terephthalate structure as the main repeating unit. A mixture of phosphorus compound component (2b) to be used is used as the catalyst system. The titanium alkoxide usable in the titanium compound component (1) is preferably selected from compounds of the formula (4). The catalyst system usable in embodiment (7) preferably satisfies the condition (a), (b) and (c) described above.

In embodiment (7), esters of terephthalic acid and ethylene glycol or oligomers thereof are prepared by transesterification of dialkyl esters of terephthalic acid with ethylene glycol, preferably dialkyl esters of terephthalic acid are preferably dimethyl terephthalate to be. Some or all of the dimethyl terephthalate subjected to the transesterification reaction may be regenerated from the shape of the polyester resin used, preferably polyethylene terephthalate resin (e.g., fibers, films and bottles).

The polyester film obtained by the process of embodiment (7) can be used for fiber production. Polyesters for this use preferably have an intrinsic viscosity (o-chlorophenol, 35 ° C.) in the range of 0.40 to 0.80, more preferably 0.45 to 0.75, particularly preferably 0.50 to 0.70. Inherent viscosities less than 0.40 are undesirable because of the poor mechanical strength of the fibers obtained. On the other hand, when the intrinsic viscosity exceeds 0.80, and when the obtained polyester is meltspun treated, the melt of the polyester may exhibit an excessively increased viscosity.

If the polyester fibers are made from the polyester resin according to embodiment (7), the fiber-making process used in embodiment (4) can be used.

The invention is illustrated by the following examples.

In the following examples and comparative examples, the polyester resins, fibers, and films obtained are subjected to the following tests.

1. Intrinsic viscosity

After 0.6 g of polyester was heat-dissolved in 50 ml of ortho-chlorophenol and cooled to room temperature, the viscosity of the obtained polyester solution was measured at 35 ° C. using an Osst viscometer and the inherent viscosity of the polyester (IV) was calculated from the data of the obtained solution viscosity.

2. Color tone of the polymer (color value L and color value b)

A sample of the polymer was melted for 10 minutes at 290 ° C. under vacuum, and the melt was molded into a 3.0 ± 1.0 mm thick plate on an aluminum plate and then quenched immediately with ice water. The obtained plate was dried at 160 ° C. for 1 hour, subjected to crystallization, and then placed on a white standard plate for colorimeter adjustment. Color value L and color value b are represented by Minolta Co., Ltd. It was measured with Hunter type color difference meter CR-200. The L value represents brightness, and the larger the value, the higher the brightness. The larger the value of b, the greater the degree of yellow tint.

3. Analysis of metal content

The concentration of titanium atoms and phosphorus atoms in the catalyst were measured in the following manner. In the case of a catalyst solution, a catalyst solution as a sample is placed in a liquid cell, and in the case of a polyester resin, a granular polyester sample containing a catalyst is heated and melted on an aluminum plate, and a molded body having a plate-like surface using a press machine. Molded into. Subsequently, each sample was analyzed quantitatively with a fluorescent X-ray spectrometer (model 3270E, manufactured by Rigaku Denki co., Ltd.).

The concentration of titanium atoms in the polymer in which titanium oxide was added as a delusterant was measured in the following manner. The sample was dissolved in hexafluoroisopropanol and the titanium oxide particles were precipitated from the solution using a centrifuge. After only the supernatant was recovered by the gradient separation method, the solvent in the recovered supernatant was evaporated to prepare a test sample, and the measurement was performed.

4. Diethylene Glycol (DEG) Content

The polymer was decomposed using hydrazine hydrate, and the content of diethylene glycol in the decomposition product was measured by gas chromatography (model: 263-70, manufactured by Hitachi, Ltd.).

5. Hue of stretched film (color value L and color value b)

Five specimens of biaxially stretched polyester film were overlaid on each other and the obtained overlapped specimens were crystallized by heat treatment for 90 minutes in a dryer at 160 ° C. Subsequently, the L value and b value of the film were determined by Color Machine Co., Ltd. It measured with the model CM-7500 colorimeter by the company.

6. Haze

The granular polymer sample was heat treated, dried in a dryer at 150 ° C. for 6 hours, melted by heating in a melt extruder at 290 ° C., extruded in sheet form on a rotary cooling drum, and then rapidly cooled and solidified , An unstretched film (sheet) having a thickness of 500 μm was produced. After a part of the obtained unstretched film having no scratches on the surface was taken as a sample, the turbidity value of the sample was determined by Nippon Denshoku Industries, Co., Ltd. It was measured with a turbidimeter (HDH-1001DP) manufactured by the company.

7. Thermal Stability (Unstretched Film)

The intrinsic viscosity value (A) of the sample of the unstretched film prepared for the measurement of turbidity, and the intrinsic viscosity value (B) of the polymer used for the preparation of the unstretched film were measured. The thermal stability of the test unstretched film was calculated from the difference value (B-A) according to the following conditions.

Exp 0-0.05 (especially excellent thermal stability)

Class 1 0.05-0.10 (excellent thermal stability)

Class 2 0.10-0.15 (good thermal stability)

Class 3> 0.15 (Poor Thermal Stability)

8. Thermal stability (biaxially oriented film)

Five specimens of biaxially stretched polyester film were overlaid on each other, the obtained overlap was crystallized by heat treatment in a dryer at 160 ° C. for 90 minutes, and the intrinsic viscosity value (A) and biaxiality of the biaxially stretched film obtained The intrinsic viscosity value (B) of the polymer used to prepare the stretched film was measured. Thermal stability was calculated from the difference (B-A) according to the following conditions.

Exp 0-0.05 (especially excellent thermal stability)

Class 1 0.05-0.10 (excellent thermal stability)

Class 2 0.10-0.15 (normal thermal stability)

Class 3> 0.15 (Poor Thermal Stability)

9. Analysis of Dimethyl Terephthalate

(a) Content of Dimethyl 2-hydroxyterephthalate

Dimethyl terephthalate was dissolved in acetone solvent and the content of dimethyl 2-hydroxyterephthalate in the solution was measured by gas chromatography (model HP5890, manufactured by Hewlett Packard; capillary column DB-17, manufactured by J & W Inc.). Then, it measured by mass spectrometry using GC-MASS (GC / mass spectrometer, model HP6890 / HP5973, the product made by Hewlett-Packard; capillary column DB-17, the product made by J & W Inc.).

10. Analysis of terephthalic acid

(a) Mass concentrations of 4-carboxybenzaldehyde, paratoluic acid and hydroxybenzaldehyde

A sample of test terephthalic acid was dissolved in 2N ammonia water, and the obtained solution was treated with a liquid chromatography system (LC-6A, STRΦDS-H column) manufactured by Shimadzu Corporation, and 4-carboxybenzaldehyde, paratoluic acid, and hydroxybenzaldehyde After separation from the solution, the mass concentration of the compound was measured.

(b) Mass concentration of monomethyl terephthalate

A test sample of terephthalic acid was subjected to high performance liquid chromatography (Equipment: Model HPLC D-7000, manufactured by Hitachi, Ltd .; Packed column: RP-18, two columns), and then the monomethyl terephthalate contained in the sample. Mass concentration was measured.

(c) mass concentration of benzoic acid

After esterifying a sample of test terephthalic acid with diazomethane, benzoic acid contained in the sample by gas chromatography treatment of the obtained ester using 10% SE-30 as a separation column, and using n-tridecane as an internal standard. The mass concentration of was measured.

11. Deposit layer formed around the spinneret

After molding the test polyester in the form of a chip, the obtained chip was melted at 290 ° C., and the melt was compressed through a spinneret having 12 spinning orifices each having a hole diameter of 0.15 mm Φ, and the melt-spinning was 600 m. It was performed continuously for 2 days at a spinning rate of / min. The height of each layer of deposits formed around the outside of the spin orifice of spinneret was then measured. Bending of the filament stream of the extruded polyester melt is promoted as the height of the deposit layer formed around the outer edge of the spinning orifice increases, resulting in poor moldability of the polyester. The height of the deposit layer formed around the spinning orifice is an index of the moldability of the polyester.

12. Tensile strength and ultimate elongation of fibers

Tensile strength and ultimate elongation of the fibers were measured according to the procedure described in JIS L 1013.

[Production Example 1]

Synthesis of Titanium Trimellitate

To the ethylene glycol solution prepared by mixing 2 parts by mass of trimellitic anhydride and 98 parts by mass of ethylene glycol, tetrabutoxytitanium was added in an amount sufficient to adjust the molar ratio to trimellitic anhydride to 0.5, The resulting mixture was reacted by holding in air for 60 minutes at a temperature of 80 ° C. under ambient atmospheric pressure. After cooling to room temperature, the product was recrystallized from 10 times the amount of acetone of the product, the precipitate obtained was collected by filtration through filter paper and dried at 100 ° C. for 2 hours to prepare the desired titanium compound. It was.

Example 1

A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol is mixed with 0.009 parts by mass of tetra-n-butyl titanate in a SUS (stainless steel) vessel where the reaction can be carried out under pressure, and the obtained mixture is The reaction was transesterified in the vessel by raising the temperature from 140 ° C. to 240 ° C. under a pressure of 0.07 MPa. Subsequently, 0.04 parts by mass of triethyl phosphonoacetate was added to the reaction mixture to complete the transesterification reaction.

The reaction product was placed in a polymerization vessel and then subjected to a polycondensation reaction by heating to a temperature of 290 ° C. under a high vacuum of 26.7 Pa (0.2 mmHg) or less, yielding an intrinsic viscosity of 0.60 and 1.5 mass% of diethylene glycol (ethylene terephthalate component). Polyethylene terephthalate resin was prepared.

The polyethylene terephthalate resin was continuously extruded in the form of a filament stream through the extrusion orifice of the melt-spinning apparatus, after which the filament stream was cooled and cut into granular pellets each about 3 mm long. The pellet obtained was dried at 180 ° C. for 3 hours and then subjected to a melt spinning procedure to prepare an unstretched filament yarn having a yarn count of 333 dtex / 36 fil. The unstretched filament yarn was then drawn at a draw ratio of 4.0 to produce a stretched multi-filament yarn having a fiber yarn count of 83.25 dtex / 36 fil.

Separately, the same dry pellet as described above was fed to a single screw kneading extruder (inner diameter: 65 mm, path length: 1000 mm, residence time: 10 minutes), and melted while gradually raising the temperature of the feed in the extruder from 280 ° C to 300 ° C. After kneading, the polyester melt was extruded through a mold to produce an unstretched film. The resulting unstretched film was biaxially stretched at 90 ° C. with a longitudinal draw ratio of 3.5 and a transverse draw ratio of 4.0, and then thermally cured at 200 ° C. to prepare a film having a thickness of 15 μm.

Example 2

A polyester resin was prepared in the same manner as in Example 1, except that the polycondensation reaction was carried out using 0.016 parts by mass of titanium trimellitate synthesized in Preparation Example 1 as a titanium compound. The properties of the obtained polyester composition fibers and the unstretched film produced using the polyester composition are shown in Table 1 below.

[Examples 3 to 9 and Comparative Examples 1 to 7]

In Examples 3 to 9 and Comparative Examples 1 to 7, respectively, the polyester resin composition was subjected to the same procedure as in Example 1, except that the type and amount of the titanium compound and the phosphorus compound were changed as shown in Table 1. Prepared by. The properties of the obtained polyester resin and the unstretched film obtained using the same are shown in Table 1.

Comparative Example 8

A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol is mixed with 0.009 parts by mass of tetra-n-butyl titanate in a SUS (stainless steel) vessel where the reaction can be carried out under pressure, and the obtained mixture is The transesterification was carried out by raising the temperature from 140 ° C. to 240 ° C. under a pressure of 0.07 MPa. Subsequently, 0.04 parts by mass of triethyl phosphonoacetate was added to the reaction mixture to complete the transesterification reaction.

After adding 0.053 parts by mass of diantimony trioxide to the obtained reaction mixture, the mixture was placed in a polymerization vessel and then subjected to a polycondensation reaction treatment by heating to a temperature of 290 ° C. under a high vacuum of 26.67 Pa (0.2 mmHg) or less, where the intrinsic viscosity was 0.60. And a polyester resin containing diethylene glycol in an amount of 1.5% by mass.

Example 10

Except for changing the amount of the titanium compound and phosphorus compound as shown in Table 1, according to the same procedure as in Example 1 to prepare a polyester resin and then to prepare a fiber, after the completion of the transesterification reaction, the average 20 mass% titanium oxide having a particle size of 0.3 mu m and 1.5 mass parts of ethylene glycol slurry were added to the obtained reaction mixture. The measurement results are shown in Table 1.

Example 11

A polyester resin and a fiber were prepared by following the same procedure as in Example 1, except that the amounts of the titanium compound and the phosphorus compound were changed as shown in Table 1, and after completion of the transesterification reaction, pentaerythritol- 0.02 parts by mass of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals Inc. under the trade name Irganox 1010) was added to the obtained reaction mixture. The measurement results are shown in Table 1.

Example 12

The slurry prepared by mixing 200 parts by mass of terephthalic acid and 105 parts by mass of ethylene glycol was placed in a reactor equipped with a stirrer, a distillation column, and a water distillation condenser. The slurry was then esterified at 270 ° C. for 240 minutes under a pressure of 0.3 MPa. After removing half of the reaction mixture obtained, the other half of the reaction mixture was maintained at a temperature of 250 ° C. and 100 parts by mass of terephthalic acid and 52 parts by mass of ethylene glycol slurry were fed to the reaction system over 150 minutes under ambient atmospheric pressure. The esterification reaction was then carried out for 90 minutes under ambient atmospheric pressure. During the reaction, the temperature of the reaction system was maintained at 250 ° C.

After removing half of the obtained reaction product, 100 parts by mass of terephthalic acid and 52 parts by mass of ethylene glycol slurry were fed, the esterification reaction was carried out, and the above procedure was repeated until the content of diethylene glycol in the reaction product was stabilized. .

After the content of diethylene glycol in the reaction product was stabilized, half of the reaction product mixture obtained by the esterification reaction was transferred to a polycondensation reaction apparatus, and 0.018 parts by mass of the titanium catalyst prepared in Preparation Example 1 and 0.040 mass of triethyl phosphate Part was added there. The polycondensation reaction was then carried out by heating the mixture to 285 ° C. under high vacuum up to 26.67 Pa, to prepare a polyester having an intrinsic viscosity of 0.62 and containing diethylene glycol in an amount of 1.0 mass%, as in Example 1 and Fibers were prepared using the polyester according to the same procedure. The measurement results are shown in Table 1.

Preparation Example 2 (Synthesis of Catalyst)

808 g of ethylene glycol and 50 g of acetic acid were placed in a 2-liter three-necked flask equipped with a function of mixing the solution with stirring, and stirred and mixed with each other. Then, 142 g of titanium tetrabutoxide was slowly added to the mixture to make clear titanium. An ethylene glycol solution of the compound was prepared. The resulting solution is referred to as "TB solution". Titanium concentration of the TB solution was measured using fluorescent X-rays. As a result, the Ti concentration was 2.0%.

In addition, 896 g of ethylene glycol was placed in a 2-liter three-necked flask equipped with a function of mixing the solution while stirring, and 224 g of triethyl phosphonoacetate was added thereto while stirring to prepare a clear solution. This solution is referred to as "TP1 solution".

Subsequently, the TP1 solution was heated to adjust the temperature of the solution to 160 ° C, and 400 g of the TB solution prepared in advance was slowly added to the TP1 solution. After the entire amount of the TB solution was added, the stirring was continued at the temperature of 160 ° C. for 1 hour to complete the reaction between the titanium compound component and the phosphorus compound component. At this time, the ratio of the amount of the TP1 solution to the amount of the TB solution was adjusted to 6.0 in terms of the ratio of the molar concentration of the phosphorus atom to the titanium atom. The reaction product was a solution soluble in ethylene glycol and had a pale yellow tint. The resulting solution is called "TT-6 catalyst".

[Manufacture example 3]

A catalyst was prepared using the same apparatus and procedure as in Preparation Example 2, except that the preparation amount and the addition amount of the TP1 solution described in Preparation Example 2 were changed as described below. Basically, 1045 g of ethylene glycol was put in the same reactor as described above, and 75 g of ethylene glycol was added thereto with stirring to prepare a clear solution. This solution is referred to as "TP2 solution". The TP2 solution was then heated to adjust the temperature of the solution to 120 ° C., and 400 g of the TB solution prepared in advance was slowly added thereto while stirring the mixture. After the entire TB solution was added, the stirring was continued for 3 hours at a temperature of 120 ° C. to complete the reaction between the titanium compound component and the phosphorus compound component. At this time, the ratio of the amount of the P1 solution to the amount of the TB solution was adjusted to 2.0 in terms of the molar concentration of the phosphorus atom to the titanium atom. As a result, a clear solution was obtained. The resulting solution is called "TT-2 solution".

Example 13

A slurry prepared by mixing 179 parts of high-purity terephthalic acid and 95 parts of ethylene glycol in a reactor containing 225 parts of an oligomer of ethylene glycol terephthalate ester was supplied at a uniform feed rate while stirring under a nitrogen atmosphere at 255 ° C. under ambient atmospheric pressure. After that, the transesterification reaction was continued for 4 hours while distilling out water and ethylene glycol produced during the reaction out of the reaction system to complete the reaction. At this time, the degree of esterification was 98% or more, and the degree of polymerization of the obtained oligomer was about 5-7.

225 parts of oligomer obtained by the esterification reaction were transferred to a polycondensation reactor, and the oligomer was mixed as a polycondensation catalyst with 0.182 parts of the titanium-phosphorus reaction product TT-6 catalyst solution described in Preparation Example 2. Then, the reaction temperature in the reaction system was raised from 255 ° C to 290 ° C, the reaction pressure was gradually reduced to 60 Pa at atmospheric pressure, and then polycondensation reaction was performed while removing water and ethylene glycol produced during the reaction out of the reaction system.

The progress of the polycondensation reaction was detected while observing the load on the stirring blade in the reaction system, and the reaction was completed when the desired degree of polymerization was reached. At this time, the polycondensation reaction time was 160 minutes. Subsequently, the reaction product in the reaction system was continuously extruded into strand form through the extrusion orifice of the melt spinning apparatus, and then the strand-shaped stream was cooled and cut to prepare granular pellets each having a length of about 3 mm. The obtained pellets were dried at 180 ° C. for 3 hours, then fed to a single screw kneading extruder (inner diameter: 65 mm, path length: 1000 mm, residence time: 10 minutes), and the temperature in the extruder was gradually reduced from 280 ° C. to 300 ° C. While rising, melt-kneading, and then melted polyester was extruded through a mold to prepare an unstretched film. The obtained non-stretched film was biaxially stretched at 90 ° C. with 3.5 times the longitudinal draw ratio and 4.0 times the transverse draw ratio, and then thermally cured at 200 ° C. to prepare a film having a thickness of 15 μm.

Example 14

A polycondensation reaction was carried out according to the same procedure as in Example 13 except that the polycondensation catalyst was replaced with the titanium-phosphorus reaction compound TT-2 solution prepared in Preparation Example 3, to prepare a film. In this case, the polycondensation reaction time was 135 minutes.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

Example 15

In addition to the titanium-phosphorus reaction compound TT-6 solution prepared in Preparation Example 2, except that tetrazol blue (abbreviated as Agent B) was added in an amount of 0.3 ppm relative to the amount of the desired polymer as a color regulator, The polycondensation reaction was carried out by the same procedure as in Example 13, to prepare a polyester film. In this case, the polycondensation reaction time was 160 minutes.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

Example 16

0.129 parts of TB solution and 0.372 parts of TP1 solution, respectively prepared in Reference Example 2, were prepared in the same procedure as in Example 13, except that the TB solution and the TP1 solution were mixed separately as a polycondensation catalyst in the reaction system. Polycondensation reaction was carried out to prepare a film. In this case, the polycondensation reaction time was 190 minutes. The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

Comparative Example 9

The polycondensation reaction was carried out by the same procedure as in Example 13 except that the amount of TT-2 was changed to 0.546 parts to prepare a film. In this case, the polycondensation reaction time was 135 minutes.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

Comparative Example 10

Example 13 except that the polycondensation catalyst was replaced with an ethylene glycol solution of 1.3% concentration of antimony trioxide, the amount of catalyst was changed to 4.83 parts, and further 0.121 parts of a 25% ethylene glycol solution of trimethyl phosphate was added as a stabilizer. The polycondensation reaction was carried out by the same procedure as in to prepare a film. In this case, the polycondensation reaction time was 130 minutes.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

Comparative Example 11

The polycondensation reaction was carried out by the same procedure as in Example 13 except that the polycondensation catalyst was replaced with the TB solution prepared in Preparation Example 2, and the amount of the catalyst was changed to 0.129 parts to prepare a film. In this case, the polycondensation reaction time was 105 minutes.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 2.

[Production Example 4]

Preparation of Recovered Dimethyl Terephthalate

200 parts by mass of ethylene glycol was placed in a 500 ml separable flask, and 50 parts by mass of polyethylene terephthalate waste consisting of 1.5 parts by mass of sodium carbonate and a crushed bottle was placed in the flask, and then the temperature was raised to 185 ° C while stirring. The conditions were maintained for 4 hours. As a result, the polyethylene terephthalate waste was dissolved and the depolymerization reaction was completed. The obtained depolymerization reaction product was concentrated by vacuum distillation and 150 parts by mass of ethylene glycol was recovered as a distillate fraction.

To the concentrated solution, 0.5 parts by mass of sodium carbonate and 100 parts by mass of methanol were mixed as a transesterification catalyst, and then the reaction mixture was stirred at a liquid temperature of 75 ° C. under ambient atmospheric pressure for 1 hour to effect esterification.

The reaction mixture obtained was cooled to 40 ° C. and then filtered through a glass filter. The crude dimethyl terephthalate recovered on the filter was mixed with 100 parts by mass of MeOH and the mixture was heated to 40 ° C., stirred, washed and filtered again through a glass filter. This wash and filtration procedure was repeated twice.

Crude dimethyl terephthalate collected on the filter was placed in a distillation apparatus and vacuum distilled under conditions of a pressure of 6.65 kPa and a reflux ratio of 0.5 to recover dimethyl terephthalate as a distillate fraction. The amount of recovered fraction was 47 parts by mass. The amount of residue in the distillation apparatus was measured to determine the amount of dimethyl terephthalate. As a result, the amount of dimethyl terephthalate was 2 parts by mass. The reactivity of dimethyl terephthalate was 93 mass% with respect to the mass of polyester introduced.

In the recovered dimethyl terephthalate purified by distillation, 0.5 mass ppm of dimethyl 2-hydroxyterephthalate was detected.

Purified recovered dimethyl terephthalate showed a purity of at least 99.9% by weight.

Example 17

A mixture of 100 parts by mass of dimethyl terephthalate prepared in Preparation Example 4 and 70 parts by mass of ethylene glycol were mixed together with 0.0088 parts by mass of tetra-n-butyl titanate in a stainless steel container capable of carrying out the reaction under pressure, and The mixture was transesterified by heating from 140 ° C. to 240 ° C. under a pressure of 0.07 MPa. Subsequently, 0.035 parts by mass of triethyl phosphonoacetate was added to the reaction mixture to complete the transesterification reaction.

After the reaction product was transferred to the polymerization vessel, a polycondensation reaction was carried out by heating to 285 ° C. under high vacuum of 26.67 Pa or less to prepare a polyester having an intrinsic viscosity of 0.63 and a content of 1.0 mass% of diethylene glycol.

The obtained ester was molded into a chip form using a melt extruder and then dried at 180 ° C. After using the obtained dry chip, an unstretched filament yarn having a fiber yarn number of 333 dtex / 36 filaments was produced by a melt spinning process, the unstretched filament yarn was stretched at a draw ratio of 4.0, and the fiber yarn number was 83.25 dtex. Elongated multi-filament yarns were prepared which were / 36 filaments. Separately, the dry chip was melt-extruded using a film forming apparatus to prepare an unstretched film, which was biaxially stretched at 90 ° C. with a longitudinal draw ratio of 3.5 and a transverse draw ratio of 4.0, followed by thermosetting at 200 ° C., A film having a thickness of 15 μm was prepared. The measurement results are shown in Table 3.

Example 18

A polyester resin was prepared according to the same procedure as in Example 17, except that 0.016 parts by mass of titanium trimellitate synthesized according to the procedure of Preparation Example 1 was used as a titanium compound, and a polyester fiber was prepared from the polyester resin. Prepared. The measurement results are shown in Table 3.

[Examples 19 to 22 and Comparative Examples 12 to 15]

In Examples 19 to 22 and Comparative Examples 12 to 15, respectively, except that compounds shown in Table 3 were used as titanium compounds and phosphorus compounds, and the amounts thereof were changed as shown in Table 3, Polyester resin compositions and fibers were prepared by the same procedure. The measurement results are shown in Table 3. In Comparative Examples 13 and 15 respectively, the polycondensation reaction rate was very slow, so the polycondensation reaction procedure ended 200 minutes after the start of the reaction.

[Comparative Example 16]

A mixture of 100 parts by mass of recovered dimethyl terephthalate prepared in Preparation Example 4 and 70 parts by mass of ethylene glycol were mixed with 0.009 parts by mass of tetra-n-butyl titanate. The obtained mixture was placed in a stainless steel vessel capable of carrying out the reaction under pressure, and the obtained mixture was subjected to transesterification while heating from 140 ° C to 240 ° C under a pressure of 0.07 MPa. Subsequently, 0.04 parts by mass of triethyl phosphonoacetate was added to the reaction mixture to complete the transesterification reaction.

After adding 0.053 parts by mass of diantimony trioxide to the reaction mixture, the mixture was transferred to a polymerization vessel and subsequently subjected to a polycondensation reaction by heating to 285 ° C. under a high vacuum of 26.67 Pa or less, having an intrinsic viscosity of 0.63 and 0.9 mass of diethylene glycol. Polyesters containing a content of% were prepared. In the same manner as in Example 17, the obtained polyester was molded into fibers and films. The measurement results are shown in Table 3.

Example 23

DMT was prepared by depolymerization of PET with ethylene glycol and transesterification of the obtained EMT with MeOH, and further hydrolysis to bring the total of TA (4-CBA, p-TA, BA and HDT to 1 ppm or less, MMT Content is 150 ppm). A slurry prepared by mixing 179 parts of recovered TA and 95 parts of ethylene glycol in a polycondensation reactor containing 225 parts of an oligomer of ethylene glycol ester of terephthalic acid was previously homogeneous while stirring the mixture under a nitrogen gas atmosphere at 255 ° C under ambient atmospheric pressure. After feeding at one feed rate, the mixture was subjected to an esterification reaction at atmospheric pressure at 275 ° C. for 4 hours while distilling out of the reaction system water and ethylene glycol produced in the reaction until the degree of esterification reached 98% or more, Oligomers having a degree of polymerization of about 5 to 7 were prepared.

A part of the oligomer prepared by the above esterification reaction was transferred to the polycondensation reactor in an amount of 225 parts by mass and mixed with 0.45 parts of the "TT-6 catalyst solution" prepared in Preparation Example 2 as the polycondensation catalyst. The reaction temperature in the reaction system was then raised from 255 ° C to 290 ° C, the reaction pressure was gradually reduced to 60 Pa at atmospheric pressure, and the water and ethylene glycol produced in the reaction were removed out of the reaction system during the reaction, while the mixture was polycondensed. The reaction was treated.

The degree of polycondensation reaction and the load on the blade for stirring in the reaction system were observed and inspected, and the reaction was terminated when the degree of polymerization was reached. In this case, the polycondensation reaction time was 160 minutes. Subsequently, the reaction product in the reaction system was continuously extruded through the extrusion orifice of the solution extrusion device into a stream in the form of strands, and then the strand-like streams were cooled and cut to prepare granular pellets each having a length of about 3 mm.

The obtained pellets were dried at 180 ° C., and then formed into sheets by melt film-forming process treatment, and then the obtained sheets were biaxially stretched at 90 ° C. with a longitudinal draw ratio of 3.5 and a transverse draw ratio of 4.0, followed by 200 ° C. Thermosetting was performed to produce a film having a thickness of 15 μm.

The properties of the obtained polyester granular pellets and polyester film are shown in Table 4.

Example 24

A polyester resin was prepared according to the same procedure as in Example 23, except that "TT-2 catalyst solution" prepared in Preparation Example 3 was used as the polycondensation catalyst instead of "TT-6 catalyst solution", and a poly An ester film was prepared. In this case, the polycondensation reaction time was 135 minutes. The properties of the obtained polyester granular pellets and polyester film are shown in Table 4.

Example 25

A polyester resin and a polyester film were prepared by the same procedure as in Example 23 except that the amount of “TT-2 catalyst solution” was changed to 1.50 parts. In this case, the polycondensation reaction time was 135 minutes. The properties of the obtained polyester granular pellets and polyester film are shown in Table 4.

Example 26

Except that 0.13 parts of "TB solution" and 0.39 parts of "TP1 solution" prepared in Production Example 2 were mixed separately in the reaction system as a polycondensation catalyst without reacting "TB solution" and "TP1 solution". Polyester resins and polyester films were prepared following the same procedure as in Example 23. In this case, the polycondensation reaction time was 190 minutes. The properties of the obtained polyester granular pellets and polyester film are shown in Table 4.

Example 27

A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol, and 0.009 parts by mass of tetra-n-butyl titanate were placed in a SUS container which can be used for the reaction under pressure, and the obtained mixture was obtained at 140 ° C. under a pressure of 0.07 MPa. The transesterification process was carried out while heating to 240 ℃. Then 0.031 parts by mass of mono-n-butyl phosphate was added to the reaction mixture to complete the transesterification reaction.

The reaction product was transferred to a polymerization vessel, and then subjected to a polycondensation reaction treatment with heating at 290 ° C. under a high vacuum of 30 Pa or less to prepare a polyester resin having an intrinsic viscosity of 0.63 and containing 1.3 mass% of diethylene glycol.

The obtained polyester resin was molded into a chip form with a melt granulator and then dried. The obtained dry chip was melt spin-treated to produce an unstretched filament yarn having a fiber yarn number of 333 dtex / 36 filaments. The unstretched filament yarn was then drawn at a draw ratio of 4.0 to obtain a stretched multi-filament yarn having a fiber yarn count of 83.25 dtex / 36 filaments.

The measurement results are shown in Table 5.

Example 28

A polyester resin and a polyester fiber were prepared by the same procedure as in Example 27 except that the titanium compound was replaced with 0.016 parts by mass of titanium trimellitate synthesized in Preparation Example 5. The measurement results are shown in Table 5.

[Examples 29 to 33 and Comparative Examples 17 to 22]

In Examples 29 to 33 and Comparative Examples 17 to 22, respectively, the polyesters were prepared according to the same procedure as in Example 27, except that each of the compounds shown in Table 5 was used as the titanium compound or the phosphorus compound in the amounts shown in Table 7 Resin and polyester fibers were prepared. The measurement results are shown in Table 5.

Example 34

The titanium compound and the phosphorus compound were replaced with the compounds shown in Table 7, and used in the amounts shown in Table 5, except that 1.5 parts by mass of 20% by mass of ethylene glycol slurry of titanium oxide was added after completion of the transesterification reaction, Polyester resins and polyester fibers were prepared according to the same procedure as in Example 27. The measurement results are shown in Table 5.

Example 35

After completion of the transesterification reaction, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals Inc. under the tradename Irganox 1010) Polyester resins and polyester fibers were prepared according to the same procedure as in Example 27 except that 0.02 parts by mass was added to the obtained reaction product. The measurement results are shown in Table 5.

Comparative Example 23

A mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol, and 0.009 parts by mass of tetra-n-butyl titanate were placed in a SUS container usable for reaction under pressure, and the obtained mixture was placed at 140 ° C and 240 ° C under a pressure of 0.07 MPa. It was transesterified with heating. Then 0.031 parts by mass of mono-n-butyl phosphate was added to the reaction mixture to complete the transesterification reaction.

After adding 0.053 parts by mass of diantimony trioxide to the reaction mixture, the mixture was transferred to a polymerization vessel, and then subjected to a polycondensation reaction by heating to 290 ° C under a high vacuum of 30 Pa or less to give an intrinsic viscosity of 0.63 and 1.3 mass% of diethylene glycol. A polyester containing the content was prepared. The polyester resin obtained was treated in the same melt spinning and stretching procedure as in Example 27 to prepare a polyester filament yarn. The measurement results are shown in Table 5.

The manufacturing method of the polyester resin of this invention makes it possible to manufacture the polyester resin which has the outstanding transparency, the outstanding color tone, and high thermal stability with high efficiency. The polyester resins, polyester fibers, polyester films and polyester bottle-shaped molded articles of the present invention all have excellent transparency and color tone, and can be manufactured with high efficiency in practice.

Claims (25)

A method for producing a poly (ethylene aromatic carboxylate ester) resin comprising polycondensing a diester of an aromatic dicarboxylic acid and ethylene glycol in the presence of a catalyst system, The catalyst system comprises one or more selected from the group consisting of: (1) a titanium compound component comprising at least one member selected from the group consisting of titanium alkoxides and reaction products of titanium alkoxides and aromatic polyvalent carboxylic acids or anhydrides thereof, and (2a) selected from compounds represented by the following formula (1): Unreacted mixtures and reaction products of phosphorus compound components comprising at least one species: [Formula 1] [Wherein, R ¹ , R ² and R ³ each independently and independently of one another represent an alkyl group having 1 to 4 carbon atoms, and X represents a —CH ₂ — group or a group represented by the following general formula (1a): [Formula 1a] ]; And (1) an unreacted mixture of the above-described titanium compound component and (2b) a phosphorus compound component comprising at least one member selected from phosphorus compounds represented by the following formulas (2) and (3): [Formula 2] [Wherein, R ⁴ represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms, n represents an integer of 1 or 2, when n represents 1, p represents an integer of 0 or 1, when n represents 2, p represents 0], [Formula 3] [Wherein m, ma and mb each independently and independently of each other represent an integer of 1 or 2]; Method for producing a poly (ethylene aromatic dicarboxylate) resin, characterized in that the catalyst system satisfies the following conditional formulas (a), (b) and (c): (a) 2 ≦ M _Ti ≦ 15 (b) 1 ≤ (M _p / M _Ti ) ≤15 (c) 10 ≦ (M _Ti + M _p ) ≦ 100 [In the above condition formulas (a), (b) and (c), M _Ti is contained in the catalyst system for the total amount (molar units) of ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester). Represents the ratio of the amount of titanium elements (millimolar units) incorporated, and M _p is the phosphorus contained in the catalyst system relative to the total amount (mol units) of ethylene aromatic dicarboxylate ester repeating units in the poly (ethylene aromatic dicarboxylate ester) Ratio of the amount of elements (millimolar units)]. The poly (ethylene aromatic dicarboxylate) resin of claim 1, further comprising preparing a diester of aromatic dicarboxylic acid and ethylene glycol by diesterization of the aromatic dicarboxylic acid and ethylene glycol. Manufacturing method. The poly (ethylene aromatic dicarboxylate ester) according to claim 1, further comprising preparing a diester of aromatic dicarboxylic acid and ethylene glycol by transesterification of the dialkyl ester of aromatic dicarboxylic acid with ethylene glycol. ) Manufacturing method of resin. 4. The transesterification reaction according to claim 3, wherein the transesterification of the aromatic dicarboxylic acid with the dialkyl ester of ethylene glycol is carried out in the presence of at least unreacted or reacted titanium compound component (1); The reaction mixture obtained from the transesterification reaction and containing a diester of aromatic dicarboxylic acid and ethylene glycol is unreacted or reacted with at least the unreacted or reacted titanium compound component (1) contained in the reaction mixture. A method for producing a poly (ethylene aromatic dicarboxylate) resin, which is polycondensed in the presence of a catalyst system comprising a compound component (2a) or an unreacted phosphorus compound component (2b). The aromatic dicarboxylic acid according to any one of claims 1 to 4, wherein the aromatic dicarboxylic acid is selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 5-sulfoisophthalate metal salt and 5-sulfoisophthalate onium salt. And manufacturing method of poly (ethylene aromatic dicarboxylate ester) resin. The dialkyl ester of aromatic dicarboxylic acid is selected from dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, diethyl terephthalate, diethyl isophthalate and diethyl naphthalate. Process for producing poly (ethylene aromatic dicarboxylate ester) resin. The method for producing a poly (ethylene aromatic dicarboxylate) resin according to claim 1, wherein the titanium alkoxide for the titanium compound component (1) is selected from a titanium compound represented by the following general formula (4): [Formula 4] [In formula, R <^5> , R <^6> , R <^7> and R <^8> respectively independently and mutually represent a C2-C10 alkyl group or a phenyl group, m <_c> represents the integer of 1-4.]. The process for producing a poly (ethylene aromatic dicarboxylate) resin according to claim 1, wherein the aromatic polyvalent carboxylic acid for the titanium compound component (1) is selected from compounds represented by the following general formula (5): [Formula 5] [Wherein, n _a represents an integer of 2 to 4]. The process for producing a poly (ethylene aromatic dicarboxylate ester) resin according to claim 3, wherein the transesterification reaction is carried out under a pressure of 0.05 to 0.20 MPa. The poly (polyether) according to claim 3, wherein the dialkyl ester of the aromatic dicarboxylic acid to be transesterified contains dimethyl terephthalate in an amount of 80 mol% or more based on the total molar amount of the dialkyl ester of the aromatic dicarboxylic acid. Ethylene Aromatic Dicarboxylate Ester) Resin. 4. The dialkyl ester of aromatic dicarboxylic acid according to claim 3, wherein the dialkyl ester of the aromatic dicarboxylic acid to be transesterified is obtained by dialkyl terephthalate recovered by depolymerization of polyalkylene terephthalate. A method for producing a poly (ethylene aromatic dicarboxylate ester) resin, containing in an amount of 70 mol% or more with respect to the total molar amount of. The method for producing a poly (ethylene aromatic dicarboxylate) resin according to claim 11, wherein the recovered dialkyl terephthalate contains 2-hydroxyterephthalic acid in a controlled content of 2 ppm or less. The process according to claim 4, wherein the catalyst system comprises an unreacted mixture of the titanium compound component (1) and the phosphorus compound component (2a) or (2b); The entire amount of the titanium compound component (1) is added to the reaction system before or at the beginning of the transesterification reaction; A method for producing a poly (ethylene aromatic dicarboxylate) resin, wherein the total amount of the phosphorus compound component (2a) or (2b) is added to the reaction system obtained from the transesterification reaction before or at the beginning of the polycondensation reaction. The process according to claim 4, wherein the catalyst system comprises the reaction product of the titanium compound component (1) and the phosphorus compound component (2a); The entire amount of the catalyst system is added to the reaction system before or at the start of the transesterification reaction; After the transesterification reaction is completed, the obtained reaction mixture is subjected to the polycondensation reaction treatment. The process for producing a poly (ethylene aromatic dicarboxylate ester) resin. The method according to claim 4, wherein, before the transesterification reaction, part of the titanium compound component (1), or part of the reaction product of the titanium compound component (1) and the phosphorus compound component (2a), or part of the phosphorus compound component (2b) Poly (ethylene aromatic dicarboxylate ester) resin, which is added to the reaction system, and at least one step during and after the transesterification reaction and before and during the polycondensation reaction, the remainder of the aforementioned catalyst components is added to the reaction system. Method of preparation. 3. The total amount of phosphorus compound component (2a) is added to the diesterization reaction system before the start of the diesterization reaction, or a part of the phosphorus compound component (2a) is added to the diesterization reaction system before the start of the reaction. , Poly (ethylene aromatic dicarboxylate ester), in which the remainder of the phosphorus compound component (2a) is added to the reaction system during and after the completion of the diesterization reaction and at one or more stages before and during the start of the polycondensation reaction. ) Manufacturing method of resin. Poly (ethylene aromatic dicarboxylate) resin manufactured by the manufacturing method of the poly (ethylene aromatic dicarboxylate ester) resin in any one of Claims 1-16. 18. The poly (ethylene aromatic dicarboxylate ester) resin according to claim 17, further comprising an antioxidant non-oil phenol compound in an amount of 1% by mass or less. The poly (ethylene aromatic dicarboxylate) resin according to claim 1, wherein the poly (ethylene aromatic dicarboxylate ester) resin contains an antimony element and a germanium element in controlled amounts of 5/1000 mol% or less, respectively. Method of preparation. A polyester fiber containing the poly (ethylene aromatic dicarboxylate ester) resin according to any one of claims 17 to 19. 21. The polyester fiber according to claim 20, wherein the poly (ethylene aromatic dicarboxylate ester) resin contains polyethylene terephthalate as a main component. The polyester film containing the poly (ethylene aromatic dicarboxylate ester) resin in any one of Claims 17-19. 23. The polyester film of claim 22, wherein the poly (ethylene aromatic dicarboxylate ester) resin contains polyethylene terephthalate as its main component. 20. A polyester bottle-shaped molded article containing the poly (ethylene aromatic dicarboxylate ester) resin according to any one of claims 17 to 19. The polyester bottle-shaped molded article according to claim 24, wherein the poly (ethylene aromatic dicarboxylate ester) resin contains polyethylene terephthalate as a main component.